Related Experiment Video
Updated: Jun 3, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
A hybrid meta on-top functional for multiconfiguration pair-density functional theory
Jie J Bao1,2, Dayou Zhang1,2, Shaoting Zhang1,3
1Department of Chemistry, Chemical Theory Center, University of Minnesota, Minneapolis, MN 55455-0431.
Abstract:
Multiconfiguration pair-density functional theory (MC-PDFT) was proposed a decade ago, but it is still in the early stage of density functional development. MC-PDFT uses functionals that are called on-top functionals; they depend on the density and the on-top pair density. Most MC-PDFT calculations to date have been unoptimized translations of generalized gradient approximations (GGAs) of Kohn-Sham density functional theory (KS-DFT). A hybrid MC-PDFT has also been developed, in which one includes a fraction of the complete active space self-consistent-field wave function energy in the total energy. Meta-GGA functionals, which use kinetic-energy densities in addition to GGA ingredients, have shown higher accuracy than GGAs in KS-DFT, yet the translation of meta-GGAs has not been previously proposed for MC-PDFT. In this paper, we propose a way to include kinetic energy density in a hybrid on-top functional for MC-PDFT, and we optimize the parameters of the resulting functional by training with a database developed as part of the present work that contains a wide variety of systems with diverse characters. The resulting hybrid meta functional is called the MC23 functional. We find that MC23 has improved performance as compared to KS-DFT functionals for both strongly and weakly correlated systems. We recommend MC23 for future MC-PDFT calculations.
More Related Videos
Related Concept Videos
Valence Bond Theory
Multicompartment Models: Overview
These models offer a more comprehensive representation of drug behavior in the body than one-compartment models. They accommodate the complexity of drug distribution,...
Hybridization of Atomic Orbitals I
Valence Bond Theory and Hybridized Orbitals
A σ bond (single bond in a Lewis structure) is a covalent bond in which the electron density is...
MO Theory and Covalent Bonding
Resonance and Hybrid Structures
Resonance Structures and Resonance Hybrids
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N–O and N=O bonds.

